Herbicidal method employing n-substituted arylimides



United States Patent 3,253,901 HERBICIDAL METHQD EMPLOYING N-SUBSTITUTED ARYLIMIDES Edward David Weil, Lewiston, and Jerome Linder, Niagara Falls, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Original application May 25, 1961, Ser. No. 112,528, now Patent No. 3,158,650, dated Nov. 24, 1964. Divided and this application Nov. 23, 1964, Ser. No. 413,346

9 Claims. (Cl. 71-23) This application is a division of our co-pending application Serial No. 112,528, filed May 25, 1961, now Patent No. 3,158,650.

This invention describes new and useful imide compositions of matter which have valuable herbicidal properties.

More particularly, this invention relates to novel-N- sttb'stitu-ted arylimides having phytotoxicity against various broadleaf weeds and annual grass. These compositions have the structure:

wherein R is a saturated or unsaturated alpha methyl substituted aliphatic radical of @from two to five carbon atoms having at least one methyl group on the alphacarbon atom, and R is chosen from the group consisting of hydrogen and saturated or unsaturated aliphatic radicals of from one to three carbon atoms, and R is a chlorinated aryl radical chosen from the group consisting of 3,4-dichlorophenyl and 3-ohloro-4 methylphenyl. The compounds of the invention are colorless oils or low-melting solids.

Representative examples of the compounds of this invention are N-formyl-N-propionyl-3,4-dichloroaniline, N-formyl-N-isobutyryl-3,4-dichloroaniline, N- formyl N-meth acrylyl-3 ,4-dichloroaniline, N-acetyl-N-propionyl-3,4-dichloroaniline, N-acetyl-N-propionyl-3-chloro-4-methylaniline, N-ace-tyl-Napropionyl-3,4-diohloroaniline, N-(3,4-di'chlorophenyl)propionmide,

N-( 3.-ch-loro-4-me-thylphenyl) propionimide,

N- 3,4-di'c'hlorophenyl isobutyrimide,

N- 3 -chloro-4-'met-hylphenyl isob-utyrimide,

N- 3,4-dichlorophenyl methacrylimide,

N- 3chloro-4-methylphenyl)methacrylimide, N-acetyl-N-methacrylyl-3,4-dichloroaniline, N-acetyl-N-methacrylyl-3-chloro-4-methylaniline, N-acetyl-'(Z-methylpentanoyl) -3,'4-dichloroaniline,

N-acetyhN- (Z methylpentanoyl) -3 -chloro-4-methyl- 3,253,91 Patented May 31, 1966 N-caproyl-N-methacrylyl-3 ,4-dicl1loroaniline, N-crotonyl-N-Ipropionyl-3,4-dichloroaniline, N crotonyl-N-isdbutyryl-3,4-diohloroaniline, N crotonyl-N-methaorylyl-3,4-diohloroaniline, N-2-ethylhexoyl-N propionyl-3,4-dichloroaniline, N-2-ethylhexoyl-N-isob-utyryl-3,4-dichloroaniline, N-2-ethylhexoyl-N-methacrylyl-3,4-dichloroaniline, N-capryl-Npropionyl,4-dichloroaniline, N-capryl-N-isobutyryl-3,4-dichloroanil-ine, N-ca'pryl-N methacrylyl-3,4-dichloroaniline, N-caprylyl-N-propionyl-3,4-dichloroaniline, N-caprylyl-N-isobutyry-l-3 ,4-dichloroani-line, N-oaprylyl-N-methacrylyl-3,4-dichloroaniline, N-caprylyl-N-2-methylpentanoyl-3-chloro-4-methylaniline.

The preferred species are those in which R is acetyl or n buty'ryl, for reasons of cost in relation to activity.

The novel compounds of this invention are especially advantageous compared to many herbicides oi the prior art (for example 2,4-D), in that they are substantially non-injurious to commercially valuable crops and turf grasses at rates of application (about one-half to ten pounds per acre), where they exert a pronounced phytotoxic effect against broadleaf perennial weeds and annual grasses. Examples of commercially important crops on which these novel imide compositions may be benerficially used without consequential injury to the crops are among other, rice, corn, carrots, potatoes, tobacco, pineapple, cotton, as well as the aforementioned desirable perennial turf grasses.

The method of the invention comprises spraying the compounds of the invention, most conveniently as an emulsion in water by the aid of an organic solvent and emusifier, onto the weed seedlings to be killed. Rates of onehalf to ten pounds of toxicant per acre are preferred, the exact rates preferable in any given situation depending on weed species, stage growth, vigor, degree of lklll" required, and other factors which will be obvious to those skilled in the art.

The compounds of the invention may be employed in combination with other herbicides and with fungicides, insecticides, growth stimulants, and fertilizers if desired. Their action may be enhanced by suitable choice of solvents, wetting agents, penetrating agents, Spreaders, stickers and synergists. The use otE the commercial spray additives known collectively as spreader-stickers is particularly to be recommended with these compounds.

The novel amides of this invention are generally made by heating stoichiometric amounts of the appropriately substituted acid chloride and the anilide or aniline until the proper number of molar equivalents of hydrogen chloride is evolved. For example, where R and R are the same the compounds are conveniently made by the prolonged heating of R NH with two moles of R COCl until two molar equivalents of hydrogen chloride are evolved. In those instances where R and R are different, the novel products are made by .the extended heating of R COCl with R CONHR or R COCl with R CONHR until one molar equivalent of hydrogen chloride is given off. Where R is hydrogen, HCOOH may be used instead of the non-existent HCOCl. Since the compounds are destined for use as herbicides they are frequently used as crudes, whose identity is confirmed by infrared and ultraviolet spectra. However, where desired, .the products may be fractionally crystallized from solvents such as aliphatic hydrocarbons, aliphatic alcohols and ketones or the like, using distillation or absorption swhere desired to remove stubborn contaminants. No solvent is necessary, although if desired, or convenient, an inert solvent such as an aromatic hydrocarbon, a chlorocarbon or a chlorohydrocarbon or nitroaromatic solvent may be expeditiously used.

3 -The reaction is operable at temperatures ranging from seventy to two hundred and fifty degrees, although the most favorable temperatures appear .to be from one hundred to two hundred degrees centigrade. Obviously,

4 EXAMPLE 2.--N-ACETYLN-PROPIONYL-3,4-

DICHLOROANILINE A solution consisting of one hundred and two parts of 3,4-dichloroacetanilide, sixty-five parts of propionyl reaction time being a function of reactants and chloride and five hundred pants of cumene is heated to re- P f F cannPt be stated wl'th Preclslon, the flux until 18.2 parts of gaseous hydrochloric acid evolves. Heme hmlts 9 tune a between one f g The cumene is distilled off leaving an oil which on crys- P hours Wlth the mterv al of four to 61g teen Ours tallization from hexane gives a white solid melting at sixty being a more usual figure. Where the lower temperatures to sixtyfive degrees cntrigrade are used, the reaction time under given conditions, W11] Analysl-S' ca1cd for C11H11C12NO2: CL 273 percent; approach the longer reacilontunes 'Whlle at higher N, 5.3 percent. Found: CI, 27.6 percent; N, 4.5 percent. peratures, the converse will usually be true. An 1101 acceptor such as pyridine is often useful in accelerating the EXAMPLES reaction and permitting lower reaction temperatures, but Using the Same techniques and equipment the f ll not essent1al to operable conditions and satlsfactory ylelds. i examples h .representative Products h are Process p P n and use 05 these novel compared from the reactants as indicated. Physical charac- POSIUOIIS are Elven the examples fOHOW- Tlllese teristics and elemental analysis established the formation furthffr j lf s 1; merely lllustratlve of vflflfklngs of the desired products in each case. Included in the folof this invention, are not to be construed as limiting the lowing list are some compounds rented to, but not i Speclficafion 0f clalms 111 any manner whatsoever cluded in, the class of compounds of the invention. These are included forcom arison ur' oses. See Table I. EXAMPLE 1.--3,4-DICHLOROPHENYL- p p p PROPIONIMIDE Herbzczdal actlvzty of compounds of Examples 1-18 A solution consisting of 32.4 parts of 3,4-dich1oro- The .compounds were dlssplved. a mlxiure of 1:1 aniline forty-seven parts of propionyl chloride and four Xylene-180p horime and emulsified m 1 with the help h dr a t f e heated at reflux um 14 6 of a commercial polyoxyethylene sorb1tan laurate-alkylun e p r S 0 Cum He 1 aryl sulfonate emulsifier. They were sprayed at four a t of gasgous b f i evolves h Qumcne 15 pounds of herbicide per acre on a mixed population of tdlstllled ofr leaving an Oil WhlCh on crystallizatlon from 1 Seedlings of broadleaf Weeds (principaily lambsquarters, g'lven Y- Parts of a solld meltlng pigweed, ragweed, and mustard), and a mixed population at slxty-elght to seventy degrees centngradeof grassy weeds, (principally crabgrass, barnyard grass, Analysis.-Calcd. for C H Cl NO C1, 25.9 percent; cheatgrass and millet). After one week, the effect of the N, 5.1 percent. Found: C1, 25.1 percent; N, 4.6 percent. herbicides was evaluated. See Table II.

TABLE I Compound No. R R2 R3 M.P., C. I O1 Calcd. 01 Found N Calcd. N Found C H C H 3,4-dichlorophenyl.-. 4 68-70 25.9 25.1 5.1 4.6

C2H5 CH3 do -5 27.3 27. 6 5. 3 4. 5

-OH(CH3)2 --OH(OH3)2 d0 -6 23.5 23.5 4.6 3.9

4 OH3 CH3 -..do 78-80 28.8 29.1 5.7 5.3 11-03111 Iii-C3117 oil 23.5 23.3 4.6 4.1

(EH3 ICE: 6 C=CH2 C=OH2 do 611 23.8 23.1 4.7 4.2

CH3 CH3 7 CE Cg do 011 19.9 19.2 3.93 3.4

CaH7 CaHv 1 8 C=OH2 -OH3 .do oil 26.1 25.9 5.15 5.0

/CH 9 -03 CH3 do oil 23.5 23.2 4.64 4.25

10 CH5 C2H5 4-chl0r0phenyl 45-65 14.6 14.6 5. 5.32

11 C H C2H5 3-chlor0phe11yi 41-2 14.6 14.2 5. 85 5.51

12 C2H5 C2H5 3-ch10r0-4-methy1- 36-7 14.0 14.2 5.60 5.50

phenyl. /CH3 13 CE CH5 do oil 14.2 14.0 5.85 5.43

14 CzH5 CH3 do oil 14.8 14.2 5.85 5.30

1 15 C=OH2 OH5 do oil 12.6 12.1 4.99 4.30

1 16 C=OH2 CaH7 3,4-dich1orophenyl... oil 23.6 23.8 4. 66 4.90

17 C2I-I5 11-03117 do oil 246 24.2 4.86 4.30

is -0H5 11-01111. ;d0 011 20.7 20.2 4.07 3.

, at four pounds per acre.

TABLE II Cpd. N Action on Broadleaf Action on Grassy Species Species A A A B A A C C O O A A B+ B+ A A B+ B C C C C B B B+ B+ A A A B A A A A B+ B SGKIZNAOOZ, kill (satisfactory control).

B=3070% kill (fair control).

C =030% kill (essentially no control).

The compounds one to eighteen were sprayed on onemonth old stands of field corn, carrots, potatoes, and rice After one week, inspection of these crops indicated no substantial injury, whereas weed seedlings of ragweed, pig weed, foxtail and cheatgrass prescut at the time of spraying were killed.

What is claimed is:

1. Method for selective post-emergence control of weeds in crops comprising the application of a phytotoxic amount of a composition containing as principal active ingredient at least one compound chosen from the group consisting of imides of the structure:

wherein R is monovalent and is selected from the group being branched with a methyl group at the alpha carbon thereof when of three to five carbon atoms, R is selected from the group consisting of hydrogen, alkyl and alkenyl of from one to nine carbon atoms and R is selected from the group consisting of 3-c-hloro-4-methylphenyl and 3,4- dichlorophenyl.

2. The method of claim 1 wherein the composition applied is N-acetyl-Npropionyl-S,4-dichloroaniline.

3. The method of claim 1 wherein the composition applied is N-n-butyryl-N-propionyl-3,4-dichloroaniline.

4. The method of claim 1 wherein the composition applied is N-n-acetyl-N-isobutyryl-3,4-dichloroaniline.

5. The method of claim 1 wherein the composition applied is N-n-butyryl-N-isobutyryl-3,4-dichloroaniline.

6. The method of claim 1 wherein the composition applied is N-acetyl-N-methacrylyl-3,4-dichloroaniline.

7. The method of claim 1 wherein the composition applied is N-n-'butyryl-N-methacrylyl-3,4-dichloroaniline.

8. The method of claim 1 wherein the composition applied is N-(3,4-dichlorophenyl)propionimide.

9. The method of claim 1 wherein the composition applied is N-(3,4-dichlorophenyl)isobutyrimide.

References Cited by the Examiner UNITED STATES PATENTS 2,226,672 12/1949 Smith 260562 X 2,648,621 8/1953 Gerjovich et a1. 260562 X 3,108,038 10/1963 Fielding et al 16730 3,119,736 1/1964 Clark et a1. 16730 FOREIGN PATENTS 1,039,779 9/ 1958 Germany.

OTHER REFERENCES Gertler et al.: US. Dept. of Agr.; Agri. Res. Suc., ARS 33-14, pages 1-12 (pages 4, 5 and 10 particularly pertinent) (1955).

LEWIS GOTTS, Primary Examiner.

JAMES O. THOMAS, Assistant Examiner. 

1. METHOD FOR SELECTIVE POST-ENGERGENCE CONTROL OF WEEDS IN CROPS COMPRISING THE APPLICATION OF A PHYTOTOXIC AMOUNT OF A COMPOSITION CONTAINING AS PRINCIPAL ACTIVE INGREDIENT AT LEAST ONE COMPOUND CHOSEN FROM THE GROUP CONSISTING OF IMIDIES OF THE STRUCTURE: 